Sol-gel SiO2/TiO2 bilayer films with self-cleaning and antireflection properties

We report here that a facile sol-gel dip-coating technique can be used to fabricate a SiO₂/TiO₂ bilayer film with self-cleaning and antireflection properties. The bottom SiO₂ layer acts as an antireflection coating due to its lower refractive index; the top TiO₂ layer acts as a self-cleaning coating generated from its photocatalysis and photo-induced superhydrophilicity. The maximal transmittance of SiO₂/TiO₂ bilayer film at normally incident light can be reached 96.7%, independent of the high refractive index and coverage of TiO₂ nanoparticles. However, the photocatalytic activity of the bilayer film shows a close dependence on coverage of TiO₂ nanoparticles. After illuminated by ultraviolet light, the SiO₂/TiO₂ bilayer films are superhydrophilic with water contact angle less than 2°, which favors greatly the self-cleaning function of the films.     

TiO2 and TiO2–SiO2 thin films and powders by one-step soft-solution method: Synthesis and characterizations

Simple soft-solution method has been developed to synthesize films and powders of TiO₂ and mixed TiO₂–SiO₂ at relatively low temperatures. This method is simple and inexpensive. Furthermore, reactor can be designed for large-scale applications as well as to produce large quantities of composite powders in a single step. For the preparation of TiO₂, we used aqueous acidic medium containing TiOSO₄ and H₂O₂, which results in a peroxo-titanium precursor while colloidal SiO₂ has been added to the precursor for the formation of TiO₂–SiO₂. Post annealing at 500 °C is necessary to have anatase structure. Resulting films and powders were characterized by different techniques. TiO₂ (anatase) phase with (1 0 1) preferred orientation has been obtained. Also in TiO₂–SiO₂ mixed films and powders, TiO₂ (anatase) phase was found. Fourier transform infrared spectroscopy (FTIR) results for TiO₂ and mixed TiO₂–SiO₂ films have been presented and discussed. The method developed in this paper allowed obtaining compact and homogeneous TiO₂ films. These compact films are highly photoactive when TiO₂ is used as photo anode in an photoelectrochemical cell. Nanoporous morphology is obtained when SiO₂ colloids are added into the solution.     

Oxidative photoelectrochemical technology with Ti/TiO2 anodes

Rutile and anatase TiO₂ films have been grown on Ti plates by thermal (500–800°C) and anodic oxidation followed by thermal annealing (400–500°C), respectively. The photoelectrochemical efficiency of these photoanodes, evaluated by current density measurements in the photooxidation of 4-methoxybenzyl alcohol in deaerated CH₃CN, has been determined. The photocurrent efficiency increases with the thickness of the TiO₂ rutile film up to 1 μm (the most efficient thickness). At the wavelengths furnished by the irradiation apparatus similar thicknesses of anatase and rutile films show nearly the same efficiencies. Anodic bias produces similar relative increases of current intensity in both crystalline forms.     

Electron microscopy studies of TiO2 micelles

The microstructural properties of nanosized TiO₂ micelles, generated in situ in a water-in-oil (w/o) microemulsion composed of water, dioctyl sulfosuccinate sodiun salt (AOT) and cyclohexane, by controlled hydrolysis of TiCl₄, were investigated. The samples were characterized by analytical electron microscopy combining electron diffraction. TiO₂ film consisted of isotropic grains of anatase. The grain sizes were 5 nm, which is in agreement with the average grain size R, previously obtained by grazing-incidence wide-angle X-ray diffraction (GIWAXD), of 5.0±1.3 nm. Grains were gathered in a number of clusters, differently oriented with respect to the electron beam.     

TiO2 photoanodes for electrically enhanced water splitting

Photoelectrochemical properties of self-organized TiO₂ nanotubes formed by electrochemical anodization of titanium sheets and their working mechanism are investigated. Formation and growth of self-organized nanotubes were carried out by Titanium anodization in acid electrolyte containing fluorides. Annealing of the samples was performed in order to increase the crystallinity of the material. Also some results obtained with samples annealed in Nitrogen atmosphere are presented. Electrochemical Impedance Spectroscopy was used to give an interpretation of the main charge transfer processes that occur at the nanotube/electrolyte interphase. The use of glycerol as hole scavenger was considered in order to improve the photoelectrochemical performance of the samples.     

Synergistic effect of Cu2O/TiO2 heterostructure nanoparticle and its high H2 evolution activity

Cu₂O/TiO₂ nanoparticles were prepared by solvothermal method, which formed the heterostructure of Cu₂O/TiO₂. Due to the heterostructure, the H₂ evolution rate under simulated solar irradiation was increasingly promoted. Meanwhile a certain amount of Cu particles which were confirmed by Transmission Electro Microscopy (TEM) and X-Ray Photoelectron Spectroscopy (XPS), formed on the surface of Cu₂O/TiO₂, and the photoactivity was accordingly further enhanced. The stabilized activity was maintained after many times irradiation. It is interesting that after a few hours irradiation the amount of Cu particles on the surface kept unchanged in the presence of Cu₂O and TiO₂. The Cu particles that formed during hydrogen generation reaction play a key role in the further enhancement of the hydrogen production activity. In this study, it is the first time to study the details on the formation of the stable ternary structure under simulated solar irradiation and their synergistic effect on the photoactivity of the water splitting.     

TiO2 films obtained by microwave-activated chemical-bath deposition used to improve TiO2-conducting glass contact

In traditional solar cells, metal-semiconductor contacts used to extract photogenerated carriers are very important. In dye-sensitized solar cells (DSSC) not much attention has been given to contact between the TiO₂ and the transparent conducting glass (TCO), which is used instead of a metal contact to extract electrons. TiO₂ layers obtained by microwave-activated chemical-bath deposition (MW-CBD) are proposed to improve TiO₂ contact to conducting glass. Spectra of incident photon to current conversion efficiency (IPCE) are obtained for two-photoelectrode TiO₂ photoelectrochemical cells. IPCE spectra show higher values when TiO₂ double layer photoelectrodes are used. In these, the first layer or contacting layer is made by MW-CBD. Best results are obtained for double layer photoelectrodes on FTO (SnO₂:F) as conducting oxide substrate. Modeling of IPCE spectra reveals the importance of electrical contact and electron extraction rate at the TiO₂/TCO interface.     

High quantum efficiency Pt/TiO2 catalyst for sacrificial water reduction

Platinum photodeposition on TiO₂ from methanolic solution of chloroplatinic acid (CPA) is investigated to determine the conditions that give optimum photocatalytic activity towards dehydrogenation of methanol. Conditions favoring nucleation of Pt islets rather than their autocatalytic growth enhance the catalytic activity. Photoplatinization from idoplatinic acid, adsorbing more strongly on TiO₂ than CPA produced more active Pt/TiO₂ catalysts. The best catalyst prepared from CPA yielded H₂ from 12.5% methanol solution at a quantum efficiency of 23.9% whereas for idoplatinic acid based catalysts, the quantum efficiency increased to 42.5%.     

Enhanced desorption properties of LiBH4 incorporated into mesoporous TiO2

LiBH₄ nano-particles are incorporated into mesoporous TiO₂ scaffolds via a chemical impregnation method. And the enhanced desorption properties of the composite have been investigated. The LiBH₄/TiO₂ sample starts to release hydrogen at 220 °C and the maximal desorption peak occurs at about 330 °C, much lower compared to the bulk LiBH₄. Furthermore, the composite exhibits excellent dehydrogenation kinetics, with 11 wt% of hydrogen liberated from LiBH₄ at 300 °C within 3 h. X-ray diffraction and Fourier transform infrared spectroscopy are used to confirm the nanostructure of LiBH₄ in the TiO₂ scaffold. This work demonstrates that confinement within active porous scaffold host is a promising approach for enhancing hydrogen decomposition properties of light-metal complex hydrides.     

Electrospun TiO2/SnO2 nanofibers with innovative structure and chemical properties for highly efficient photocatalytic H2 generation

Innovative TiO₂/SnO₂ nanofibers were fabricated via electrospinning an innovated precursor solution and used for photocatalytic H₂ generation. The nanofibers exhibited greatly enhanced H₂ evolution rate compared to bare TiO₂ nanofiber and P25. The enhanced efficiency of the TiO₂/SnO₂ nanofibers was attributed to its excellent synergistic properties: (1) its good mesoporosity; (2) the red-shift of absorbance spectra to enhance light absorbance capability; (3) its long nanofibrous structure and (4) anatase TiO₂ – rutile TiO₂ – rutile SnO₂ ternary junctions favorable for the separation of electrons and holes. Based on our experimental results, the optimum ratio of TiO₂/SnO₂ nanofibers with 3% Sn demonstrated the highest efficiency in H₂ generation.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.     

CuCr2O4/TiO2 heterojunction for photocatalytic H2 evolution under simulated sunlight irradiation

CuCr₂O₄/TiO₂ heterojunction has been successfully synthesized via a facile citric acid (CA)-assisted sol-gel method. Techniques of X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectrum (UV-vis DRS) have been employed to characterize the as-synthesized nanocomposites. Furthermore, photocatalytic activities of the as-obtained nanocomposites have been evaluated based on the H₂ evolution from oxalic acid solution under simulated sunlight irradiation. Factors such as CuCr₂O₄ to TiO₂ molar ratio in the composites, calcination temperature, photocatalyst mass concentration, and initial oxalic acid concentration affecting the photocatalytic hydrogen producing have been studied in detail. The results showed that the nanocomposite of CuCr₂O₄/TiO₂ is more efficient than their single part of CuCr₂O₄ or TiO₂ in producing hydrogen. The optimized composition of the nanocomposites has been found to be CuCr₂O₄·0.7TiO₂. And the optimized calcination temperature and photocatalyst mass concentration are 500 °C and 0.8 g l⁻¹, respectively. The influence of initial oxalic acid concentration is consistent with the Langmuir model.     

Significantly improved dehydrogenation of LiAlH4 catalysed with TiO2 nanopowder

The effects of TiO₂ nanopowder addition on the dehydrogenation behaviour of LiAlH₄ have been studied. The 5 wt.% TiO₂-added LiAlH₄ sample showed a significant improvement in dehydrogenation rate compared to that of undoped LiAlH₄, with the dehydrogenation temperature reduced from 150 °C to 60 °C. Kinetic desorption results show that the added LiAlH₄ released about 5.2 wt% hydrogen within 30 min at 100 °C, while the as-received LiAlH₄ just released below 0.2 wt.% hydrogen within same time at 120 °C. From the Arrhenius plot of the hydrogen desorption kinetics, the apparent activation energy is 114 kJ/mol for pure LiAlH₄ and 49 kJ/mol for the 5 wt.% TiO₂ added LiAlH₄, indicating that TiO₂ nanopowder adding significantly decreased the activation energy for hydrogen desorption of LiAlH₄. X-ray diffraction and Fourier transform infrared analysis show that there is no phase change in the cell volume or on the Al-H bonds of the LiAlH₄ due to admixture of TiO₂ after milling. X-ray photoelectron spectroscopy results show no changes in the Ti 2p spectra for TiO₂ after milling and after dehydrogenation. The improved dehydrogenation behaviour of LiAlH₄ in the presence of TiO₂ is believed to be due to the high defect density introduced at the surfaces of the TiO₂ particles during the milling process.     

Electrospun Pt/TiO2 hybrid nanofibers for visible-light-driven H2 evolution

One-dimensional (1D) Pt/TiO₂ hybrid nanofibers (HNFs) with different concentrations of Pt were fabricated by a facile two-step synthesis route combining an electrospinning technique and calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) results showed that the Pt nanoparticles (NPs) with the size of 5–10 nm were well dispersed in the TiO₂ nanofibers (NFs). Further investigations from the UV–Vis diffuse reflectance (DR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that some Pt ions were incorporated into the TiO₂ lattice as Pt⁴⁺ state, which contributed to the visible light absorption of TiO₂ NFs. Meanwhile, the Pt²⁺ ions existing on the surface of Pt NPs resulted in the formation of Pt–O–Ti bond at Pt NPs/TiO₂ NFs interfaces that might serve as an effective channel for improving the charge transfer. The as-electrospun Pt/TiO₂ HNFs exhibited remarkable activities for photocatalytic H₂ evolution under visible light irradiation in the presence of l-ascorbic acid as the sacrificial agent. In particular, the optimal HNFs containing 1.0 at% Pt showed the H₂ evolution rate of 2.91 μmol h⁻¹ and apparent quantum efficiency of 0.04% at 420 nm by using only 5 mg of photocatalysts. The higher photocatalytic activity could be ascribed to the appropriate amount of Pt ions doping and excellent electron-sink effect of Pt NPs co-catalysts.     

Formation of ultrafast-switching viologen-anchored TiO2 electrochromic device by introducing Sb-doped SnO2 nanoparticles

Ultrafast-switching viologen-anchored TiO₂ electrochromic device (ECD) was developed by introducing Sb-doped SnO₂ (Sb_xSn_1−xO₂, ATO) as counter electrode (CE), and the switching behavior of the fabricated ECD was investigated as a function of Sb-doping concentration. About 9-nm-sized Sb_xSn_1−xO₂ (x=0–0.3) nanoparticles were synthesized by a solvothermal reaction of tin (IV) chloride and antimony (III) chloride at 240 °C, and employed to fabricate 2.4-μm-thick transparent CE. Working electrode (WE) was formed from the 7-nm-sized TiO₂ nanoparticle by a doctor blade method, and the thickness of the nanoporous TiO₂ electrode was 4.5 μm. The phosphonated viologen, bis(2-phosphonylethyl)-4,4′-bipyridinium dibromide, was then adsorbed on the prepared films for the construction of the ECD. The response time was strongly dependent on the doping concentration of Sb in ATO, and the fastest switching response was observed at 3 mol%. At this composition, the coloration time was 5.7 ms, and the bleaching time was 14.4 ms, which is regarded as one of the best results so far reported.     

Elevated temperature cycling stability and electrochemical impedance of LiMn2O4 cathodes with nanoporous ZrO2 and TiO2 coatings

In this study, nanoporous zirconia (ZrO₂) and titania (TiO₂) coatings are shown to stabilize the cycling performance of lithium-ion batteries with LiMn₂O₄ spinel cathodes. The effect of firing temperature on the coating pore size is discussed and the resulting performance of the coated cathodes is evaluated. Stabilization mechanisms, such as neutralization of acidic electrolytes by ZrO₂ and TiO₂ coatings, are examined. It is proposed that the establishment of a complex nanoporous network for lithium-ion transport results in a more uniform current distribution at the particle surface, thereby suppressing capacity fade that may be associated with surface instabilities of the spinel electrode.     

Electrochemical performance of mesoporous TiO2 anatase

Mesoporous TiO₂ was prepared via a sol–gel method from an ethylene glycol-based titanium-precursor in the presence of a non-ionic surfactant at pH 2. Only the anatase structure was detected after annealing, while the BET specific surface area was measured as being 90 m² g⁻¹ with a rather monomodal pore diameter close to 5 nm. Electrochemical performances were investigated by cyclic voltammetry and galvanostatic techniques. Mesoporous TiO₂ exhibits excellent rate capability (184 mAh g⁻¹ at C/5, 158 mAh g⁻¹ at 2C, 127 mAh g⁻¹ at 6C, and 95 mAh g⁻¹ at 30C) and good cycling stability.     

Visible-light-driven TiO2 catalysts doped with low-concentration nitrogen species

Visible-light-driven nitrogen-doped TiO₂ was synthesized using a novel nitrogen-ion donor of hydrazine hydrate. Low-concentration (0.2 at%) nitrogen species and Ti³⁺ were detected in the TiO₂-based photocatalyst by X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) spectroscopy. The trace amount of Ti–N would contribute to the minor band-gap narrowing of about 0.02 eV. Those nitrogen-containing species, especially the NO₂²⁻ species, form surface states, which make the catalysts possible to degrade 4-chlorophenol (4-CP) under visible irradiation (λ>400 nm). Moreover, Ti³⁺ species induce oxygen vacancy states between the valence and the conduction bands, which would also contribute to the visible response. The photocatalytic activity of the nitrogen-doped TiO₂ catalyst was thought to be the synergistic effect of nitrogen and Ti³⁺ species. The catalysts showed higher photocatalytic activity for degradation of 4-CP than pure TiO₂ under not only visible but also UV irradiation. The visible response and the higher UV activity of the nitrogen-doped TiO₂ make it possible to utilize solar energy efficiently to execute photocatalysis processes.     

Morphological, optical and photocatalytic properties of TiO2–Fe2O3 multilayers

Morphological, optical and photocatalytic properties of TiO₂, Fe₂O₃ and TiO₂–Fe₂O₃ samples (formed by 1, 3 and 5 coatings) were studied. The layers were deposited on glass substrate by the sol–gel method. The catalytic activity of the samples was studied by the photodecomposition of methylene blue (MB) under visible light illumination. The FTIR results indicate that all samples present surface OH radicals that are bound either to the Ti or Fe atoms. This effect is better visualized at larger number of coatings in the TiO₂–Fe₂O₃/glass systems. Also, two mechanisms are observed during the photodecomposition of the MB.     

Cu2O/Cu/TiO2 nanotube Ohmic heterojunction arrays with enhanced photocatalytic hydrogen production activity

Cu₂O/Cu/TiO₂ nanotube heterojunction arrays were prepared by assembling Cu@Cu₂O core-shell nanoparticles on TiO₂ nanotube arrays (NTAs) using a facile impregnation-reduction method. SEM and TEM results show that Cu@Cu₂O plate-like nanoparticles with tens of nanometers in size are confined inside TiO₂ NTAs. Only the outmost several nanometers of the nanoparticles are Cu₂O and the predominant inner of the nanoparticles are Cu metals. Cu L₃VV Auger spectra of Cu₂O/Cu/TiO₂ NTAs suggest that Cu metals are enveloped by at least several nanometers Cu₂O on the surface, which further confirms the Cu@Cu₂O core shell structure of Cu nanoparticles. The ability of light absorption of Cu₂O/Cu/TiO₂ NTAs is enhanced. The range of absorption wavelengths changes from 400 to 700 nm due to the surface plasmon response of Cu metals core and Cu₂O nanoparticles shell. The photocatalytic hydrogen production rate of Cu₂O/Cu/TiO₂ heterojunction arrays is enhanced when compared with those of Cu₂O/TiO₂ NTAs and TiO₂ NTAs under UV light. Moreover, a stable H₂ generation property was obtained under visible light (λ gt; 400 nm). The Cu metal core is believed to play a key role in the enhancement of photocatalytic properties of Cu₂O/Cu/TiO₂ nanotube heterojunction arrays.